EP0959148B1 - Procede de production de pellicules de diamant faisant appel a un systeme de synthese en phase gazeuse - Google Patents

Procede de production de pellicules de diamant faisant appel a un systeme de synthese en phase gazeuse Download PDF

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Publication number
EP0959148B1
EP0959148B1 EP97933934A EP97933934A EP0959148B1 EP 0959148 B1 EP0959148 B1 EP 0959148B1 EP 97933934 A EP97933934 A EP 97933934A EP 97933934 A EP97933934 A EP 97933934A EP 0959148 B1 EP0959148 B1 EP 0959148B1
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Prior art keywords
substrate
hydrogen
flow
methane
gas
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Expired - Lifetime
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EP97933934A
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German (de)
English (en)
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EP0959148A4 (fr
EP0959148A2 (fr
Inventor
Alexandr Tursunovich Rakhimov
Nikolai Vladislavovich Suetin
Vladimir Anatolevich Samorodov
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OOO "Vysokie Tekhnologii"
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J9/00—Apparatus or processes specially adapted for the manufacture, installation, removal, maintenance of electric discharge tubes, discharge lamps, or parts thereof; Recovery of material from discharge tubes or lamps
    • H01J9/02—Manufacture of electrodes or electrode systems
    • H01J9/022—Manufacture of electrodes or electrode systems of cold cathodes
    • H01J9/025—Manufacture of electrodes or electrode systems of cold cathodes of field emission cathodes
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/02—Pretreatment of the material to be coated
    • C23C16/0227—Pretreatment of the material to be coated by cleaning or etching
    • C23C16/0236—Pretreatment of the material to be coated by cleaning or etching by etching with a reactive gas
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/02—Pretreatment of the material to be coated
    • C23C16/0272—Deposition of sub-layers, e.g. to promote the adhesion of the main coating
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
    • C23C16/26—Deposition of carbon only
    • C23C16/27—Diamond only
    • C23C16/271—Diamond only using hot filaments
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/56—After-treatment
    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B25/00—Single-crystal growth by chemical reaction of reactive gases, e.g. chemical vapour-deposition growth
    • C30B25/02—Epitaxial-layer growth
    • C30B25/10—Heating of the reaction chamber or the substrate
    • C30B25/105—Heating of the reaction chamber or the substrate by irradiation or electric discharge
    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
    • C30B29/02—Elements
    • C30B29/04—Diamond

Definitions

  • This invention pertains to a method for forming highly effective films to be used for field electron emitters which could be applied for manufacturing of flat panel displays, electron microscopes, microwave electronics and a number of other applications.
  • the base of using of the diamond as cold emitters is a negative affinity of diamond [F.J.Himsel et al. Phys. Rev. B, 20(2) 624, 1979]. All the existing attempts to produce a highly effective electron emitter from polycrystalline diamond films are not to be considered as positive ones, in particular due to the very low emission sites density. Emission sites density of such films was not higher than 10 3 per CM 2 , but for obtaining of the full color display it is necessary to reach 10 5 .
  • the technical goal is invention of a method for producing films with a highly effective emission properties to be used for cathode manufacturing for the full color displays, exactly to produce nano crystalline diamond films with highly effective emission characteristics.
  • the CVD method comprising a heating the metal filaments and substrates under the hydrogen flow, introducing a carbon containing gas into the flow and deposition.
  • diamond film on the substrate in hydrogen - carbon containing gas mixture evacuating surplus of graphite phase; deposition is going on the substrate heated up to 650-900C through the protective grid screen located between the filament heated up to 1800-2800C and the substrate, under carbon containing gas concentration in gas flow 2-10%; the methane under concentration 2-8% could be used as carbon containing gas in gas flow, and in the case of the silicon substrate before deposition the natural oxide should be removed in hydrogen flow under the filament and the substrate temperatures needed for deposition, the silicon carbide layer should be created on the substrate by introducing in gas flow 5-20% methane during 4-20 minutes, after this the methane concentration should be decreased up to 2-8%, after this there should be a deposition process and evacuating surplus of graphite phase.
  • This method can produce diamond films both on conductive and insulating substrates, in particular on the silicon substrate which is a good conductor under the used temperature range.
  • the main role of the protective grid screen is to change the relation between concentrations of chemical radicals near surface of the substrate due to effective recombination on the grid walls some of radicals (especially hydrogen atoms).
  • the protective grid which is being placed between the substrate and filaments, is made of a materials resistant to high temperature (up to 1500C) and resistant to sputtering.
  • the area of the plate having holes will normally correspond to about the area of the film to be grown on the substrate. Distance between holes and the diameter of the holes should be properly chosen in order to obtain the maximum grid transparence.. If the diameter of holes is less than 0.1 mm the transparency of the grid decreases, if the holes diameter is more than 5 mm in a grid 1 to 2 mm thick, the effect of the grid on chemical radical concentration near the substrate surface begins to decrease The minimal thickness of the grid is limited only mechanical resistance of the grid. The increasing of the thickness resulted in enhancement of grid role on the chemical components what gives decreasing of the film growth rate.
  • the distance between the grid and the substrate is not limited on a low end so the grid could be placed just on the substrate (in this case a diamond film would have a grid patterning). Maximal distance is limited by the filament temperature which could be higher 2000C.
  • the metal filament is heated up to the temperature range 1800-2800C. Under the temperatures lower than 1800C all the chemical processes have a too low rate, under the temperatures higher than 2800C there is a fast carbide transformation of the filament resulted in a filament breaking.
  • the filaments should be made of a materials resistant to high temperature (up to 2800C), chemically resistant and resistant to the sputtering. Generally it could be tungsten or tantalum or renium wire which length should be practically selected.
  • the increasing of the filament thickness resulted in increasing of chemical filament activation, however it should be noted that the thickness value could be limited by used power supply source.
  • the surface could be coated either graphite or diamond with a large grain structure which have a bad emission properties.
  • FIG.1 shows a sketch of a gas phase (CVD) reactor suitable for the method of this invention and Fig.2. showing a scanning electron microscope image of a diamond film grown by the method of this invention.
  • CVD gas phase
  • Deposition system comprises reactor tube (1), preferably made from quartz, closed and sealed by flanges (2) and (3). Flanges (3) additionally to the water cooling have isolated current plugs in (4) for an electrical power supply from the sources (5) and (6) to the hot filament (7) and a substrate heater (8).
  • the substrate (9) is placed on the substrate holder (10) and is separated from the metal wire (7) by the protective grid (11) which is placed on a special holder (12). The distance between grid (11) and substrate (8) may be determined by thickness of holder (12).
  • Vacuum pump (13) provides vacuum pumping.
  • Working gases are supplied through a number of electronic mass-flow controllers (14), buffer mixture volume (15) and gas flow regulator (16).
  • the temperature of the filament is controlled by the optical pyrometer (it is not shown on the figure), the substrate temperature is controlled by thermocouple (17), mounted into the substrate holder (10).
  • the thermocouple contact is realized by the isolated current plug in which is similar to the (4).
  • Vacuum chamber (1) is pumped up to necessary vacuum. After evacuating the chamber the hydrogen gas is injected into the reactor through the mass-flow controller (14) in order to keep needed flow value. After the hydrogen flow rate achieves required value a gas pressure could be hold under the needed value by using controller (16). After this power supplies are switch on to heat substrate heater (8) and filament (7). The substrate and filament temperatures can be regulated by the power supply voltage. After a time needed to allow the substrate and filament to reach the required temperatures, the carbon containing gas (for example methane ) is injected into the reactor through the individual flow meter (14) under selected with the hydrogen proportion. From this moment the deposition process begins.
  • the hydrogen containing gas for example methane
  • the deposition process should be stopped by interrupting a carbon containing gas flow (for example the methane) and all the steps should be made in reverse order.
  • a carbon containing gas flow for example the methane
  • the metal filament was made from the tungsten wire with the thickness 0.5mm.
  • Example 1 The diamond film deposition process on silicon substrate.
  • the substrate temperature under deposition process was in range 680-850C.
  • the filament temperature was in the range 2100-2200C.
  • the distance between the filament and the grid was 1-6 mm, between the substrate and grid 0.1-2 mm. It should be noted that increasing of the filament-.substrate distance is decreasing a deposition rate very sharp since the chemically active radicals are generated near the filament.
  • Process of deposition on silicon substrate comprises the following steps:
  • the hydrogen gas is injected into the reactor up to the pressure 1-11 kPa (10-80 Torr).
  • the power supplies are switch on to heat the substrate heater and the filament.
  • the silicon oxide was removed in the hydrogen during 4-20 minute
  • the methane gas is injected into the reactor under the relative concentration 5-20%.
  • the silicon carbide layer is formed on the substrate surface. This layer is needed to improve the adhesion of a diamond film to the silicon substrate and to improve electron injection performances from the silicon substrate to the diamond film.
  • the methane concentration in the gas mixture is reduced to the range 2%- 8% and the diamond film is grown on the substrate surface with the rate 0.5 microns/hour.
  • the methane flow was interrupted and film annealing in the hydrogen was performed during 4-10 minutes for removing of graphite layer from the film surface
  • Example 2 The diamond film deposition process on the metal substrate.
  • the process has a certain difference in comparison with the deposition process on the silicon substrate. It is due the different chemical activity of the metal and the silicon.
  • the processes of chamber pumping, gas injection and filament heating are the similar to the Example 1. However the stage of the oxide removal is not needed. Following stage is the methane injection (2-5%) into the gas flow and the diamond film is growing with the rate 0.2-0.5 microns/hour. Since the such metal as molybdenum, tungsten, tantalum have a high rate of carbides formation the special stage for carbide layer formation could be omitted. After the film was grown up to the necessary thickness (usually 1 micron) the methane flow was interrupted and followed by film annealing in the hydrogen for removal of graphite layer from the film surface.
  • a thin nano crystalline diamond film was grown on the substrate.
  • Fig.2 a scanning electron microscope image of the surface texture is shown of a sample of thin nano crystalline diamond film deposited by the method of this invention. The same fact was confirmed by the scanning tunneling microscopy. X-ray diffractometry showed that a typical value of the grain size is about 10-50 nm. Graphs of electrical current vs. electrical field strength showed that the "turn-on" emission voltage is very low - a few V/micron. It was reached the emission current density 100 mA/cm 2 , emission sites density 10 5 per cm 2 The characteristics of diamond films deposited on the metal substrates are similar to the ones for the diamond films deposited on the silicon substrates.
  • the films produced by the above described way could be applied as cold cathode emitters in flat panel displays. These films could be used in cathode luminescent light sources for projectors, jumbotron pixels where the high brightness is required.
  • the diamond cold emitters could be used in vacuum electronic devices.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Mechanical Engineering (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Crystals, And After-Treatments Of Crystals (AREA)

Abstract

Cette invention se rapporte au domaine de la production de pellicules d'une grande efficacité qui sont destinées à des émetteurs de champs d'électrons. Cette invention concerne plus particulièrement la production de pellicules de diamant qui possèdent d'excellentes caractéristiques d'émission électronique. La déposition des pellicules de diamant sur le substrat se fait dans un mélange d'hydrogène et d'un gaz contenant du carbone, ce gaz étant présent dans le flux gazeux selon une proportion allant de 2 à 10 %. La déposition se fait à travers un écran de protection de type grille qui est situé entre un filament métallique et le substrat. Le filament métallique et le substrat sont préalablement chauffés dans le flux d'hydrogène à des températures allant respectivement de 1800 à 2800° C et de 650 à 900° C. Après obtention d'une pellicule de diamant d'une épaisseur voulue, on élimine les excédants de phase graphite dans l'hydrogène. On peut utiliser du méthane en qualité de gaz contenant du carbone, ceci selon une concentration dans le flux gazeux allant de 2 à 8 %. Juste avant d'effectuer la déposition de la couche de diamant sur le substrat de silicium, on élimine l'oxyde de silicium naturel présent sur ce dernier dans un flux d'hydrogène, le serpentin et le substrat se trouvant à des températures permettant d'effectuer ladite déposition. On crée ensuite sur le substrat une couche de carbure de silicium en envoyant du méthane dans le flux gazeux selon une proportion allant de 5 à 20 %, et pendant une durée allant de 4 à 20 min. Une fois la pellicule de diamant déposée à l'aide d'une concentration de 2 à 8 % de méthane dans le flux gazeux, on procède à l'élimination des excédants de phase graphite dans le flux d'hydrogène pendant une durée allant de 3 à 10 min.

Claims (3)

  1. Procédé de formation de films de diamant en phase gazeuse comprenant : le chauffage d'un filament métallique et d'un substrat dans un courant d'hydrogène, l'injection dans le courant d'hydrogène d'un gaz contenant du carbone, la formation d'un film de diamant sur le substrat dans le mélange d'hydrogène et de gaz contenant du carbone, l'élimination du surplus de la phase graphite, de l'hydrogène, dans le but d'obtenir des films de diamant nano-cristallins présentant des caractéristiques d'émission d'électrons hautement efficaces, avec augmentation de la température du filament métallique jusqu'à une valeur située entre environ 1800 et 2800 C, augmentation de la température du substrat jusqu'à environ 650 - 900 C, positionnement d'un écran à grille protectrice entre le substrat et le filament, à une concentration du gaz contenant du carbone dans le courant gazeux de 2 - 10 %.
  2. Procédé selon la revendication 1, dans lequel Je gaz contenant du carbone est le méthane, qui est introduit à une concentration se situant dans la plage de 2-8 % dans le courant gazeux.
  3. Procédé selon la revendication 2, dans lequel le substrat est constitué de silicium, le réacteur est d'abord rempli avec le courant d'hydrogène pour éliminer l'oxyde de silicium naturel dans les plages de température du filament métallique et du substrat nécessaires pour le dépôt du film, une couche de carbure de silicium se trouve formée sur le substrat par introduction de méthane à la concentration de 5 -20 % dans le courant gazeux pendant 4 à 20 minutes, la quantité de méthane dans le mélange gazeux est réduite à 2-8%, le film de diamant est formé, le surplus de phase graphite est éliminé.
EP97933934A 1996-07-16 1997-07-15 Procede de production de pellicules de diamant faisant appel a un systeme de synthese en phase gazeuse Expired - Lifetime EP0959148B1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
RU96113270/09A RU2158037C2 (ru) 1996-07-16 1996-07-16 Способ получения алмазных пленок методом газофазного синтеза
RU96113270 1996-07-16
PCT/RU1997/000229 WO1998002027A2 (fr) 1996-07-16 1997-07-15 Procede de production de pellicules de diamant faisant appel a un systeme de synthese en phase gazeuse

Publications (3)

Publication Number Publication Date
EP0959148A2 EP0959148A2 (fr) 1999-11-24
EP0959148A4 EP0959148A4 (fr) 2001-09-12
EP0959148B1 true EP0959148B1 (fr) 2003-04-09

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EP97933934A Expired - Lifetime EP0959148B1 (fr) 1996-07-16 1997-07-15 Procede de production de pellicules de diamant faisant appel a un systeme de synthese en phase gazeuse

Country Status (7)

Country Link
EP (1) EP0959148B1 (fr)
JP (1) JP2001506572A (fr)
KR (1) KR100532864B1 (fr)
AU (1) AU3711297A (fr)
DE (1) DE69720791T2 (fr)
RU (1) RU2158037C2 (fr)
WO (1) WO1998002027A2 (fr)

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Publication number Priority date Publication date Assignee Title
RU2194328C2 (ru) * 1998-05-19 2002-12-10 ООО "Высокие технологии" Холодноэмиссионный пленочный катод и способ его получения
US6181055B1 (en) 1998-10-12 2001-01-30 Extreme Devices, Inc. Multilayer carbon-based field emission electron device for high current density applications
KR100360686B1 (ko) * 2000-07-27 2002-11-13 일진나노텍 주식회사 탄소나노튜브 또는 탄소나노섬유 합성용 기상합성장치 및이를 사용한 합성 방법
AU2000278552A1 (en) * 2000-10-04 2002-04-15 Extreme Devices Incorporated Carbon-based field emission electron device for high current density applications
US6624578B2 (en) 2001-06-04 2003-09-23 Extreme Devices Incorporated Cathode ray tube having multiple field emission cathodes
DE102004012044A1 (de) * 2004-03-11 2005-09-29 Infineon Technologies Ag Verfahren zum Herstellen einer im Wesentlichen aus Kohlenstoff bestehenden Schicht, eine Sondeneinheit, ein Verfahren zum Herstellen einer Sondeneinheit und ein Rasterkraftmikroskop mit einer Sondeneinheit
RU2653036C2 (ru) * 2016-08-24 2018-05-04 Федеральное государственное бюджетное учреждение науки Институт теплофизики им. С.С. Кутателадзе Сибирского отделения Российской академии наук (ИТ СО РАН) Способ осаждения алмазных плёнок из термически активированной смеси газов и реактор для его реализации
RU2656627C1 (ru) * 2017-06-27 2018-06-06 Степан Андреевич Линник Способ селективного осаждения поликристаллического алмазного покрытия на кремниевые основания
CN111747414B (zh) * 2020-06-18 2023-03-03 太原理工大学 多层碳化硅/二氧化硅/金刚石复合自支撑膜及制备方法

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US3714334A (en) * 1971-05-03 1973-01-30 Diamond Squared Ind Inc Process for epitaxial growth of diamonds
SU966782A1 (ru) * 1979-11-05 1982-10-15 Предприятие П/Я М-5912 Способ изготовлени многоострийного автокатода
JPS63159292A (ja) * 1986-12-23 1988-07-02 Showa Denko Kk ダイヤモンド膜の作製方法
US5006203A (en) * 1988-08-12 1991-04-09 Texas Instruments Incorporated Diamond growth method
US5141460A (en) * 1991-08-20 1992-08-25 Jaskie James E Method of making a field emission electron source employing a diamond coating
US5129850A (en) * 1991-08-20 1992-07-14 Motorola, Inc. Method of making a molded field emission electron emitter employing a diamond coating
US5474021A (en) * 1992-09-24 1995-12-12 Sumitomo Electric Industries, Ltd. Epitaxial growth of diamond from vapor phase

Also Published As

Publication number Publication date
RU2158037C2 (ru) 2000-10-20
DE69720791T2 (de) 2004-02-12
WO1998002027A2 (fr) 1998-01-22
WO1998002027A3 (fr) 1998-02-19
JP2001506572A (ja) 2001-05-22
EP0959148A4 (fr) 2001-09-12
KR20000023788A (ko) 2000-04-25
EP0959148A2 (fr) 1999-11-24
DE69720791D1 (de) 2003-05-15
KR100532864B1 (ko) 2005-12-02
AU3711297A (en) 1998-02-09

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